Ink set and textile printing method

Abstract

One aspect of the present invention is an ink set comprising an ink composition containing a black pigment and a treatment liquid. The ink composition is applied to a textile printing image formation region in an amount of 20 g / m2 to 80 g / m2, and the treatment liquid is applied thereto at a mass ratio of 0.5 to 1 with respect to the ink composition application amount.

Description

Ink set and printing method

[0001] The present invention relates to an ink set and a textile printing method.

[0002] Printing of objects to be printed, such as fabrics, with ink compositions has been studied, and when printing with ink compositions, an extremely large number of properties are required for the resulting printed products.

[0003] For example, when printing using a pigment ink, excellent color development is required. Patent Document 1 describes a technology for improving color development by using a pigment printing reaction liquid containing a polyvalent metal salt, a cationic polymer, a polyhydric alcohol having a boiling point of 250°C or higher, and water in a pigment printing treatment liquid. Patent Document 2 also describes a technology for improving color development by using an inkjet ink that uses a polycarbonate-based urethane resin as a binder resin in printing.

[0004] JP 2023-128434 A JP 2019-206628 A

[0005] An ink set according to one aspect of the present disclosure is an ink set including an ink composition containing a black pigment and a treatment liquid, wherein the ink composition is applied to an image forming area of ​​a textile printing target at a rate of 20 g / m ２ 80g / m or more ２ and the treatment liquid is applied at a mass ratio of 0.5 to 1 relative to the amount of the ink composition applied.

[0006] A textile printing method according to another aspect of the present disclosure includes applying a treatment liquid to an image formation area to be printed, and applying an ink composition containing a black pigment to the image formation area to which the treatment liquid has been applied, wherein the amount of the ink composition applied to the image formation area is 20 g / m. ２ 80g / m or more ２ and the mass ratio of the treatment liquid to the ink composition is 0.5 or more and 1 or less.

[0007] Fig. 1 is a side view showing an example of the configuration of a part of an inkjet textile printing apparatus using an ink set according to one embodiment of the present invention. Fig. 2 is a side view showing another example of the configuration of a part of an inkjet textile printing apparatus using an ink set according to one embodiment of the present invention. Fig. 3 is a schematic cross-sectional view of an inkjet printer that can use an ink set according to one embodiment of the present invention.

[0008] As mentioned above, when printing using pigment ink, excellent color development is required, but ink using black pigment in particular has the problem that color development is inferior to ink using dye. Specifically, ink using black pigment has the problem that the brightness is too bright.

[0009] However, in the textile printing methods described in Patent Documents 1 and 2, there is no description whatsoever about color development in textile printing using a black pigment, and there is room for improvement in color development.

[0010] In addition, in textile printing methods, there is a demand for not only color development but also improvement in abrasion fastness, and further for suppressing stiffness of the printed fabric and improving texture such as feel to the touch.

[0011] The ink set and textile printing method of the present disclosure can provide printed textiles that have excellent color development, excellent rub fastness, and good texture.

[0012] Hereinafter, embodiments of the present invention will be described, but the present disclosure is not limited to these.

[0013] <Ink Set> The ink set in this embodiment is an ink set including an ink composition containing a black pigment and a treatment liquid, and the ink composition is applied to an image forming area of ​​a textile printing target at an amount of 20 g / m ２ 80g / m or more ２The treatment liquid is applied in a mass ratio of 0.5 to 1 relative to the amount of the ink composition applied. By using such an ink set, it is possible to obtain a printed item that has excellent color development, excellent rub fastness (dry rub fastness and wet rub fastness), and good texture (feel to the skin, etc.).

[0014] In this embodiment, the subject of printing may be, for example, a product containing fiber, or may be a product made of fiber. Examples of the subject of printing include woven fabrics, knitted fabrics, nonwoven fabrics, and braided fabrics. Examples of the fiber include natural fibers such as cotton, silk, wool, and linen; chemical fibers such as polyester, acrylic, polyurethane, polyamide, rayon, cupra, and acetate; and blends thereof. The subject of printing may contain one of these fibers alone or two or more of them in combination. More specifically, examples of the subject of printing include cotton fabric, silk fabric, linen fabric, polyester fabric, acetate fabric, rayon fabric, polyamide fabric, and polyurethane fabric. The subject of printing may also be polyester tropical fabric, which is a fabric made of plain woven polyester thread. The subject of printing may be one of these fibers alone or two or more of them in combination.

[0015] In this specification, the image forming area to be printed, to which the ink composition and the treatment liquid have been applied, is referred to as a printed item.

[0016] [Ink Composition] The ink composition in this embodiment contains a black pigment and is applied at a rate of 20 g / m2 to the image forming area of ​​the textile printing target. ２ 80g / m or more ２The ink composition is applied as follows. Since the ink composition is applied to the image forming area of ​​the textile printing target, it is preferably a textile printing ink composition. Furthermore, the ink composition can be applied to the image forming area of ​​the textile printing target using any method known to those skilled in the art, such as inkjet printing or spraying, but from the viewpoint of obtaining a printed textile product having excellent color development, excellent rub fastness, and good texture, it is preferably applied using inkjet printing. In other words, the ink composition is preferably an inkjet ink composition.

[0017] The ink composition is preferably applied in an amount of 30 g / m to the image forming area to be printed. ２ 70g / m or more ２ More preferably, the coating is applied at a rate of 40 g / m or less. ２ 60g / m or more ２ It is applied as follows:

[0018] The ink composition preferably further contains a resin, an aqueous medium, and an organic solvent. The resin preferably contains a first resin having an elongation of 500% to 750% and a tensile strength of 25 MPa to 40 MPa, and a second resin having an elongation of 250% to 550% and a tensile strength of 55 MPa to 90 MPa. By using such an ink composition, it is possible to more reliably obtain excellent fastness (dry rub fastness and wet rub fastness) and a good texture on the fabric in the obtained printed product.

[0019] Each component contained in the ink composition will be described in more detail below.

[0020] (Black Pigment) The black pigment contained in the ink composition of this embodiment may be, for example, a dispersible black pigment that is dispersed in water. From the viewpoint of obtaining an ink composition that is excellent in image density, hue, and color stability, the volume median diameter (D50) of the black pigment is preferably 30 nm or more and 250 nm or less, and more preferably 70 nm or more and 160 nm or less.

[0021] In this specification, the volume median diameter (D50) is a median diameter measured using a laser diffraction / scattering particle size distribution analyzer ("LA-950" manufactured by Horiba, Ltd.).

[0022] As the black pigment of this embodiment, conventionally known organic black pigments and inorganic black pigments can be used. Examples include organic black pigments such as aniline black, and inorganic black pigments such as carbon black. More specifically, examples include C.I. Pigment Black 1 and C.I. Pigment Black 7. If necessary, these pigments may be used alone or in combination of two or more.

[0023] In this embodiment, the content of the black pigment is preferably 2% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 8% by mass or less, relative to the total amount of the ink composition. By having the black pigment content of 2% by mass or more, excellent color development can be more reliably ensured. Furthermore, by having the black pigment content of 10% by mass or less, excellent abrasion resistance can be more reliably ensured.

[0024] Furthermore, the ink composition of this embodiment preferably contains an anionic pigment. This causes an electrical reaction and aggregation between the cationic polymer and the anionic pigment contained in the treatment liquid used for textile printing together with the ink composition on the surface of the textile to be printed, thereby suppressing the penetration of the resin contained in the ink composition into the printed textile. In other words, the resin can be prevented from penetrating into the gaps between fibers and bonding the fibers together, thereby more reliably improving the texture of the textile printed with the ink composition. Examples of the anionic pigment include pigments having an anionic group such as a carboxy group, a sulfonic acid group, a phosphate group, a phosphonic acid group, a phenylphosphonic acid group, and a phenylcarboxy group (pigments into which an anionic group has been introduced).

[0025] In this embodiment, the black pigment is preferably dispersed in a dispersion containing a pigment dispersion resin and used as a pigment dispersion.

[0026] Examples of pigment dispersion resins that can be used in this embodiment include alkali-soluble resins such as styrene-acrylic acid copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-maleic acid half ester copolymer, vinylnaphthalene-acrylic acid copolymer, and vinylnaphthalene-maleic acid copolymer. These may be used alone or in combination of two or more, as necessary.

[0027] (Resin) The resin of this embodiment preferably includes at least two types of resins (a first resin and a second resin). The first resin has an elongation of 500% to 750% and a tensile strength of 25 MPa to 40 MPa. The second resin has an elongation of 250% to 550% and a tensile strength of 55 MPa to 90 MPa. By combining a first resin with a high elongation and a relatively low tensile strength with a second resin with a relatively low elongation and a high tensile strength, it is possible to more reliably obtain excellent abrasion fastness and a good texture in the resulting printed textile.

[0028] In this embodiment, the terms "elongation" and "tensile strength" refer to values ​​measured by the measurement methods shown in the examples described below.

[0029] The first resin more preferably has an elongation of 600% or more and 700% or less, and a tensile strength of 35 MPa or more and 40 MPa or less.

[0030]

[0033] The first resin may be any resin having the elongation and tensile strength as described above, but it is preferable to use one supplied in the form of an aqueous emulsion (a water-dispersible resin). Considering the ease of preparing an ink composition by blending with a pigment, a solvent, and water, and the need to disperse the resin as uniformly as possible in the ink composition, it is preferable to add the resin to the ink composition in the form of a resin emulsion in which the resin is stably dispersed in water as a dispersion medium.

[0031] Examples of water-dispersible resins that can be used in this embodiment include polyurethane resins, styrene-acrylic resins, silicone resins, polyester resins, acrylic resins, etc. Copolymers of two or more of the above resins, such as styrene-acrylic resin-polyester resin copolymers and styrene-acrylic resin-urethane resin copolymers, can also be used.

[0032] The resin may have a reactive functional group or may be a polymer containing a crosslinking agent, which is thought to result in an increase in molecular weight or a curing reaction due to crosslinking of a portion of the resin and strong bonding with the object to be printed when transferred to the object to be printed, resulting in excellent adhesion.

[0033] As the first resin, it is preferable to use a resin having a molecular structure that maintains flexibility even after curing, such as a urethane resin. If the amount of fixer resin added is increased to improve the adhesion stability of the ink composition to the object to be printed, the flexibility of the printed item may decrease, resulting in a stiff texture and deterioration of the texture. Therefore, by using a resin having a molecular structure that maintains flexibility even after curing, it is possible to more reliably obtain a good texture in the printed item.

[0034] The urethane resin is not particularly limited, and examples thereof include polyurethane resins obtained by reacting a polyol with a polyisocyanate. More specifically, for example, polymers formed by urethane bonds between polyols such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly(ethylene adipate), poly(diethylene adipate), poly(propylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), poly-ε-caprolactone, poly(hexamethylene carbonate), and silicone polyols and isocyanates such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate, or block copolymers, random copolymers, graft copolymers, and the like thereof can be used.

[0035] The styrene-acrylic resin may be a combination of one or more selected from a styrene-(meth)acrylic acid copolymer and a styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer. Examples of the (meth)acrylic acid ester include benzyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, phenol EO-modified (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

[0036] The silicone resin may be a modified silicone oil of the side chain type, one end type, both ends type, or both ends type of side chain.

[0037] Examples of the polyester resin include polymers formed by ester bonds of divalent carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, sodium sulfoisophthalate, succinic acid, adipic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, and dimer acid, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyrrolimetic acid, and dihydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polytetraethylene glycol, 1,4-cyclohexanedimethanol, and ethylene oxide adducts of bisphenol A, trimethylolpropane, and trivalent or higher polyhydric alcohols such as pentaerythritol, and block copolymers, random copolymers, and graft copolymers thereof.

[0038] Next, the elongation of the second resin is more preferably 250% or more and 300% or less, and the tensile strength is more preferably 60 MPa or more and 90 MPa or less.

[0039] The second resin can be any resin having the elongation and tensile strength as described above, without any particular limitation. Specifically, the various resins listed above as the first resin can be used.

[0040] The first resin and the second resin may be the same type of resin or different types of resin. When the same type of resin is used for the first resin and the second resin, the compatibility between the resins can be improved, and a uniform coating film can be obtained. Among the resins exemplified above, it is preferable to use polyurethane resin as the first resin and the second resin from the viewpoint of obtaining a printed product with a good texture.

[0041] When the ink composition of this embodiment contains the first resin and the second resin, the mass ratio of the first resin to the second resin (second resin / first resin) is preferably 0.2 to 1.7. This more reliably achieves both good rub fastness and texture, and is thought to result in particularly excellent dry rub fastness. A more preferred range for this mass ratio is 0.3 to 1.2, and an even more preferred range is 0.4 to 1.0.

[0042] When the ink composition of this embodiment contains the first resin and the second resin, the total content of the first resin and the second resin in the ink composition is preferably 6% by mass or more relative to the total amount of the ink composition from the viewpoint of obtaining high rub fastness, and 12% by mass or less from the viewpoint of improving texture, more preferably 7% by mass or more and 11% by mass or less, and even more preferably 8% by mass or more and 10% by mass or less.

[0043] The resin in this embodiment preferably contains the first resin and the second resin, and may further contain another resin as long as the effects of the present disclosure are not impaired.

[0044] (Aqueous Medium) The aqueous medium that can be contained in the ink composition of this embodiment is a medium containing water as a main component. The aqueous medium may function as a solvent or as a dispersion medium. Specific examples of the aqueous medium include water and a mixture of water and a polar solvent. Examples of polar solvents contained in the aqueous medium include methanol, ethanol, isopropyl alcohol, butanol, and methyl ethyl ketone. These may be used alone or in combination of two or more. When the ink composition contains the aqueous medium, the content of the aqueous medium in the ink composition is preferably 5% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 60% by mass or less.

[0045] (Organic Solvent) The organic solvent that can be contained in the ink composition of this embodiment is not particularly limited, and examples thereof include polyols and glycol ethers. In particular, the ink composition preferably contains a polyol, as this allows the viscosity of the ink composition to be suitably adjusted. The polyol is preferably a diol or triol. Examples of diols include glycol compounds, more specifically, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Examples of triols include glycerin. These can be used alone or in combination of two or more. When the ink composition contains the organic solvent, the content of the organic solvent in the ink composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less, from the viewpoint of preventing the ink composition from drying out.

[0046] (Additives and Manufacturing Method) The ink composition according to this embodiment may contain a surfactant in addition to the above-described components (resin, black pigment, aqueous medium, and organic solvent). Preferred examples of the surfactant include acetylene glycol-based surfactants and silicone-based surfactants.

[0047] When the ink composition contains a surfactant, the content of the surfactant in the ink composition is usually preferably about 0.01 to 3.0% by mass, and more preferably 0.1 to 1.0% by mass, relative to the total amount of the ink composition.

[0048] Furthermore, the ink composition of this embodiment may further contain known additives (more specifically, a dissolution stabilizer, an anti-drying agent, an antioxidant, a viscosity adjuster, a pH adjuster, an anti-mold agent, etc.) as necessary.

[0049] When the ink composition contains a pH adjuster, the pH adjuster is not particularly limited, but examples include sodium hydroxide, triethanolamine, dimethylaminoethanol, etc. By including a pH adjuster in the ink composition, it becomes possible to adjust the pH of the ink composition to a desired value.

[0050] When the ink composition contains a pH adjuster, the content of the pH adjuster in the ink composition is preferably 0.01% by mass or more and 1% by mass or less, and more preferably 0.05% by mass or more and 0.2% by mass or less, relative to the total amount of the ink composition. However, the content of the pH adjuster is not limited to the above range and may be adjusted appropriately depending on, for example, the desired pH of the ink composition.

[0051] The ink composition used in this embodiment is produced by, for example, using a mixer to mix a resin, a black pigment, an aqueous medium, an organic solvent, and optional components (e.g., surfactants, etc.). The mixing time is, for example, 1 minute to 30 minutes. After mixing, the mixture is centrifuged to remove coarse particles such as foreign matter and dust, and then filtered to remove fine particles, thereby obtaining the ink composition of this embodiment.

[0052] [Treatment Liquid] The treatment liquid in this embodiment is a pretreatment liquid that is applied to the image formation area of ​​the textile printing target prior to the ink composition. Since the treatment liquid is applied to the image formation area of ​​the textile printing target, it is preferably a textile printing treatment liquid. Furthermore, the treatment liquid can be applied to the image formation area of ​​the textile printing target using any method known to those skilled in the art, such as inkjet printing or spraying, but from the viewpoint of obtaining a printed textile product with excellent color development, excellent rub fastness, and good texture, it is preferably applied using inkjet printing. In other words, the treatment liquid is preferably an inkjet treatment liquid.

[0053] The treatment liquid is applied at a mass ratio (treatment liquid / ink composition) of 0.5 to 1, preferably 0.6 to 1, and more preferably 0.7 to 1, relative to the amount of the ink composition applied.

[0054] The treatment liquid of this embodiment preferably contains a water-soluble cationic polymer and an organic acid salt. With this configuration, the water-soluble cationic polymer and the organic acid salt react and aggregate with the black pigment contained in the ink composition to be subsequently applied, thereby more reliably ensuring excellent color development. When the treatment liquid contains the water-soluble cationic polymer and the organic acid salt, the total content of the water-soluble cationic polymer and the organic acid salt in the treatment liquid is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 35% by mass or less, and even more preferably 13% by mass or more and 30% by mass or less, based on the total amount of the treatment liquid.

[0055] When the treatment liquid contains the water-soluble cationic polymer and the organic acid salt, by setting the total content of the water-soluble cationic polymer and the organic acid salt to 5 mass% or more with respect to the total amount of the treatment liquid, the water-soluble cationic polymer and the organic acid salt are likely to react and aggregate with the black pigment contained in the ink composition, and excellent color development can be more reliably ensured.

[0056] When the total content of the water-soluble cationic polymer and the organic acid salt is 40% by mass or less relative to the total amount of the treatment liquid, the treatment liquid spreads uniformly over the object to be printed, making it less likely to cause uneven density. Furthermore, when the treatment liquid is used for inkjet printing, contamination of the fabric feed belt in an inkjet printing device can be suppressed. Furthermore, because the water-soluble cationic polymer and the organic acid salt are easily dissolved in the treatment liquid, the occurrence of white streaks due to excessively high cohesive force can be suppressed. Meanwhile, while it is believed that the occurrence of such white streaks can be suppressed by reducing the application amount, a small application amount can result in the treatment liquid not spreading over the object to be printed, which can result in the occurrence of streaks.

[0057] When the treatment liquid contains the water-soluble cationic polymer, the content of the water-soluble cationic polymer is preferably 0.3% by mass or more and 35% by mass or less, based on the total amount of the treatment liquid. By setting the content within this range, it is possible to ensure a balance between the color development, texture, and abrasion fastness of the printed textile. The content of the water-soluble cationic polymer is more preferably 0.5% by mass or more and 29.5% by mass or less, and even more preferably 1% by mass or more and 20% by mass or less, based on the total amount of the treatment liquid.

[0058] When the treatment liquid contains the organic acid salt, the content of the organic acid salt is preferably 0.1% by mass or more and 25% by mass or less, based on the total amount of the treatment liquid. By setting the content within this range, it is possible to ensure a good balance between the color development, texture, and abrasion fastness of the printed textile. The content of the organic acid salt is more preferably 5% by mass or more and 23% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less, based on the total amount of the treatment liquid.

[0059] Furthermore, in the treatment liquid of this embodiment, it is more preferable that the content of the organic acid salt is greater than the content of the water-soluble cationic polymer. This is thought to more reliably improve the texture of the printed fabric when used for textile printing. In this case, the content of the organic acid salt is preferably 1 to 15% by mass with respect to the total amount of the treatment liquid. This is thought to more reliably improve the texture of the printed fabric when used for textile printing.

[0060] The water-soluble cationic polymer contained in the treatment liquid of this embodiment is not particularly limited as long as it is a water-soluble, positively charged cationic polymer, but examples thereof include cationic polymers such as ammonium-containing polymers, amine-containing polymers, polyallylamine, polyvinylamine, polyimine, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyridine, aminoacetalized polyvinyl alcohol, ionene polymers, polyvinylimidazole, polyvinylbenzylphosphonium, polyalkylallylammonium, polyamidine, and polyamine sulfone. Among these, from the viewpoint of obtaining superior color development, particularly preferred examples include quaternary ammonium-containing polymers, diallyldimethylammonium sulfur dioxide copolymers, diallyldimethylammonium chloride acrylamide copolymers, diallyldimethylammonium chloride polymers, dimethylamine-ammonia-epichlorohydrin polycondensates, and dimethylamine-ammonia-epichlorohydrin polycondensates. These may be used alone or in combination of two or more.

[0061] The water-soluble cationic polymer may contain succinate anions, which can further suppress yellowing of the resulting printed textile (e.g., yellowing that may occur when the resulting printed textile is heated). That is, the water-soluble cationic polymer may contain succinic acid as a counter ion. Specifically, the water-soluble cationic polymer may form a salt with succinate anions. More specifically, at least a portion of the anions of the water-soluble cationic polymer may be ion-exchanged with succinate anions. Furthermore, when the water-soluble cationic polymer forms a salt with succinate anions, water solubility can be increased, and therefore the content of the water-soluble cationic polymer can be increased. In this way, when the content of the water-soluble cationic polymer is increased, the coagulation property of the ink composition with respect to coloring materials such as pigments contained in the ink composition can be further improved, resulting in a printed textile with superior color development and texture. Therefore, a printed textile with superior color development and texture can be obtained while suppressing yellowing.

[0062] The weight average molecular weight of the water-soluble cationic polymer used in this embodiment is not particularly limited, but is preferably about 1000 to 10000. If the molecular weight is in this range, it is considered that ejection properties from an inkjet head will be good when inkjet printing is performed.

[0063] The treatment liquid of this embodiment preferably further contains succinic acid. The succinic acid may be contained in the form of succinate ions. Specifically, as described above, the succinic acid may be contained in the water-soluble cationic polymer in the form of succinate anions as counter ions. By including succinic acid in the treatment liquid, the effect of stabilizing the water-soluble cationic polymer can be obtained.

[0064] Examples of the organic acid salts contained in the treatment solution of this embodiment include magnesium salts of organic acids, ammonium salts of organic acids, calcium salts of organic acids, aluminum salts of organic acids, sodium salts of organic acids, and potassium salts of organic acids. These organic acid salts may contain water of hydration in their raw material form. Examples of the magnesium salts of organic acids used in this embodiment include magnesium acetate, magnesium lactate, magnesium sulfate, and trimagnesium phosphate. The ammonium salts of organic acids used in this embodiment are not particularly limited, but from the viewpoint of solubility in water, ammonium formate, ammonium acetate, ammonium propionate, ammonium oxalate, ammonium tartrate, ammonium lactate, ammonium succinate (diammonium succinate), diammonium malonate, ammonium malate, ammonium citrate, diammonium hydrogen citrate, triammonium citrate, and ammonium L-glutamate are preferred. These salts may be used alone or in combination of two or more. Among these, ammonium formate, ammonium acetate, ammonium propionate, ammonium lactate, magnesium acetate, and magnesium lactate are preferred from the viewpoint of color development.

[0065] The treatment liquid of this embodiment may further contain a metal salt other than the organic acid salts. By containing a metal salt, the above-mentioned flocculation effect can be obtained, and it is thought that washing fastness can also be improved when used for textile printing.

[0066] The metal salt that can be used in this embodiment is preferably a polyvalent metal salt composed of divalent or higher valent metal ions and anions, and examples of divalent or higher valent metal ions include ions of calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, iron, and the like.

[0067] Specific examples of metal salts include calcium acetate, aluminum acetate, calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, calcium hydroxide, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, copper nitrate, etc. These metal salts may be used alone or in combination of two or more. Among these, calcium acetate, etc. is more preferably used from the viewpoint of excellent water solubility. These metal salts may have water of hydration in the raw material form.

[0068] When the treatment liquid of this embodiment contains the metal salt, the content thereof is preferably about 0.1 to 5 mass % relative to the total amount of the treatment liquid. The lower limit of the content of the metal salt is more preferably 0.5 mass % or more, and even more preferably 1 mass % or more, relative to the total amount of the treatment liquid. The upper limit of the content of the metal salt is more preferably 4 mass % or less, and even more preferably 3 mass % or less, relative to the total amount of the treatment liquid.

[0069] In addition, in the treatment liquid of this embodiment, it is preferable that the content of the organic acid salt is greater than the content of the metal salt. This is thought to improve the washing fastness described above while also improving the feel. In this case, it is preferable that the content of the metal salt is 0.1 to 5 mass % relative to the total amount of the treatment liquid, and the content of the organic acid salt is 1 to 15 mass % relative to the total amount of the treatment liquid, from the viewpoint of more reliably obtaining excellent washing fastness and a good feel.

[0070] In the treatment liquid of this embodiment, the remainder other than the above-mentioned components is usually water or an aqueous solvent containing water and an organic solvent.

[0071] Examples of the organic solvent that can be contained in the treatment liquid of this embodiment include glycols, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, ethers, vegetable oils, etc. Examples of the aqueous solvent include polyhydric alcohols, ether compounds of polyhydric alcohols, nitrogen-containing compounds, alcohol compounds, sulfur-containing compounds, propylene carbonate, and ethylene carbonate.

[0072] Examples of the polyhydric alcohol include a first diol compound having 5 to 8 carbon atoms, a second diol compound having 2 to 4 carbon atoms, 1,2,6-hexanetriol, glycerin, trimethylolpropane, sugar alcohols (e.g., xylitol), and sugars (e.g., xylose, glucose, and galactose).

[0073] Examples of the first diol compound include 2-methylpentane-2,4-diol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, and 1,2-hexanediol.

[0074] Examples of the second diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butylene glycol, and diethylene glycol.

[0075] Examples of the ether compounds of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and ethylene oxide adducts of diglycerin.

[0076] Examples of the nitrogen-containing compound include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, and triethanolamine.

[0077] Examples of the alcohol compound include ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol.

[0078] Examples of the sulfur-containing compound include thiodiethanol, thiodiglycerol, sulfolane, and dimethyl sulfoxide.

[0079] Among the above organic solvents, it is preferable to use glycols such as propylene glycol.

[0080] The organic solvents described above may be used alone or in combination of two or more.

[0081] When the treatment liquid of this embodiment contains the organic solvent, the content thereof is preferably 3% by mass or more and 50% by mass or less, based on the total amount of the treatment liquid. By containing the organic solvent in this range, it is possible to provide a treatment liquid with a viscosity that allows stable ejection. Another advantage is that the treatment liquid can be prevented from drying out.

[0082] Furthermore, the treatment liquid of this embodiment may contain a surfactant for the purpose of adjusting the surface tension to an appropriate level. There are no particular limitations on the surfactant that can be used, and examples include nonionic surfactants, cationic surfactants, and anionic surfactants.

[0083] When the treatment liquid of this embodiment contains a surfactant, the content thereof is preferably 0.1% by mass or more and 5% by mass or less, based on the total amount of the treatment liquid. By containing the surfactant in this range, it is possible to provide a treatment liquid with a surface tension that allows stable ejection.

[0084] The treatment liquid of the present embodiment may contain other additives as long as the effects of the present disclosure are not impaired. Examples of additives include a dissolution stabilizer, a drying inhibitor, an antioxidant, a viscosity adjuster, a pH adjuster, and an anti-mold agent.

[0085] The pH of the treatment liquid is not particularly limited, and the lower limit is preferably 7 or higher from the viewpoint of suppressing corrosion of the inkjet printing apparatus (e.g., inkjet head, etc.). The upper limit of the pH of the treatment liquid is preferably 9.5 or lower, more preferably 8 or lower, from the viewpoint of further suppressing deterioration in the texture of the resulting printed textile. The pH of the treatment liquid can be adjusted, for example, by the composition of the treatment liquid. More specifically, when the treatment liquid contains the organic acid salt and the metal salt, the pH of the treatment liquid can be adjusted by the type and content of these salts, or by the type and content of the pH adjuster added to the treatment liquid. The pH of the treatment liquid can be measured, for example, using a known pH meter.

[0086] [Post-treatment liquid] In addition to the ink composition and the treatment liquid, the ink set in this embodiment may also include a post-treatment liquid. The post-treatment liquid is applied to the image formation area of ​​the textile printing target after an image has been formed in the image formation area of ​​the textile printing target with the ink composition.

[0087] The post-treatment liquid is not particularly limited as long as it is a treatment liquid that can be used as a post-treatment liquid in a textile printing method. Examples of the post-treatment liquid include a post-treatment liquid containing a silicone oil emulsion. By including the silicone oil emulsion, the post-treatment liquid can improve the slipperiness of the surface of the textile to be printed and improve friction fastness. Furthermore, the post-treatment liquid may contain an aqueous medium as a main component (e.g., 50% by mass or more), and may also contain a surfactant, if necessary.

[0088] The silicone oil is not particularly limited, and can be exemplified by dimethylsilicone oil, amino group-containing silicone oil, carboxy group-containing silicone oil, phenolic hydroxy group-containing silicone oil, silanol group-containing silicone oil, epoxy group-containing silicone oil, mercapto group-containing silicone oil, phenyl group-containing silicone oil, long-chain alkyl group-containing silicone oil etc.The silicone oil emulsion can be the emulsion that contains one of these silicone oils alone, or can be the emulsion that contains two or more of them in combination.In addition, the silicone oil emulsion itself can be used alone, or can be used in combination of two or more.

[0089] When the post-treatment liquid contains the silicone oil emulsion, the content of the silicone oil emulsion is not particularly limited, but from the viewpoint of improving friction fastness, it is preferable that the content of the silicone oil emulsion be, for example, 1% by mass or more and 35% by mass or less with respect to the post-treatment liquid.

[0090] The aqueous medium contained in the post-treatment liquid is not particularly limited as long as it contains water. Examples of the aqueous medium include the water contained in the treatment liquid described above, or the same aqueous medium containing water and an organic solvent. The type and content of the organic solvent can be similarly described. The aqueous medium may function as a solvent or a dispersion medium in the post-treatment liquid. The content of the aqueous medium is not particularly limited, and may be the remainder of the silicone oil emulsion, etc., and is preferably, for example, 50% by mass or more and 90% by mass or less, and more preferably 55% by mass or more and 70% by mass or less, relative to the post-treatment liquid.

[0091] The post-treatment liquid may contain a surfactant for the purpose of adjusting the surface tension, etc. Furthermore, by containing a surfactant in the post-treatment liquid, the wettability of the post-treatment liquid with respect to the object to be printed is also improved. The surfactant is not particularly limited, and may be any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, etc.

[0092] When the post-treatment liquid contains a surfactant, the content of the surfactant is not particularly limited, but is, for example, preferably 0% by mass or more and 5% by mass or less, and more preferably 0.1% by mass to 5% by mass, relative to the mass of the post-treatment liquid.

[0093] The post-treatment liquid may further contain known additives (more specifically, a dissolution stabilizer, a drying inhibitor, an antioxidant, a viscosity adjuster, a pH adjuster, an anti-mold agent, etc.) as needed.

[0094] The post-treatment liquid is produced by, for example, using a stirrer to mix the silicone oil emulsion, the aqueous medium, and optional components. The mixing time is not particularly limited, but is preferably, for example, from 1 minute to 30 minutes.

[0095] The post-treatment liquid is applied in an amount of 1 g / m to the image forming area of ​​the textile printing object. ２ 20g / m or more ２ It is preferable to apply the following:

[0096] The ink set according to this embodiment is adjusted for inkjet printing and is therefore particularly suitable for use in inkjet textile printing. For example, the ink set according to this embodiment can be used in an inkjet textile printing apparatus 10 (described later), but can also be used in textile printing machines other than inkjet textile printing.

[0097] <Textile Printing Method> The textile printing method of this embodiment includes applying a treatment liquid to an image formation area to be printed, and applying an ink composition containing a black pigment to the image formation area to which the treatment liquid has been applied. The amount of the ink composition applied to the image formation area is 20 g / m. ２ 80g / m or more ２ and the mass ratio of the treatment liquid to the ink composition is 0.5 or more and 1 or less.

[0098] According to the textile printing method of the present embodiment, the above-described treatment liquid and ink composition are applied in predetermined amounts to the image forming area of ​​the textile printing target, thereby making it possible to obtain a printed textile product that has excellent color development, excellent friction fastness, and a good texture.

[0099] The treatment liquid and ink composition in the textile printing method can be explained in the same manner as the treatment liquid and ink composition in the ink set described above, and therefore further explanation will be omitted.

[0100] The printing method of this embodiment can be carried out, for example, by an inkjet printing apparatus 10 as shown in FIG.

[0101] 1 may be, for example, an inkjet printing apparatus that applies (ejects) a treatment liquid onto an image formation area of ​​a printing target, and then applies (ejects) an ink composition containing a black pigment onto the image formation area to which the treatment liquid has been applied, thereby forming an image on the printing target. The inkjet printing apparatus 10 includes a treatment liquid head 1, an ink head 2, and a mounting table 4. The ink head 2 may include a first ink head 2a, a second ink head 2b, a third ink head 2c, and a fourth ink head 2d.

[0102] The treatment liquid head 1 ejects the treatment liquid onto at least the image formation area of ​​the object to be printed P. That is, the treatment liquid is applied to at least the image formation area of ​​the object to be printed P. The treatment liquid used here is the treatment liquid in the ink set described above. There are no particular limitations on the treatment liquid head 1, but examples include a piezo type head and a thermal inkjet type head.

[0103] The ink head 2 ejects an ink composition onto an image formation area of ​​the printing object P. That is, the ink composition is applied to at least the image formation area of ​​the printing object P. The ink composition used here includes the ink composition in the above-mentioned <Ink Set>. The number of ink heads in the ink head 2 is not limited, and may be one or more, as long as it is equipped with ink heads that eject the ink compositions in the above-mentioned <Ink Set>. For example, if the ink head 2 has four ink heads, the ink head 2 includes a first ink head 2a, a second ink head 2b, a third ink head 2c, and a fourth ink head 2d, and each ink head ejects a different color ink (e.g., yellow ink, magenta ink, cyan ink, and black ink). The ink head 2 is not particularly limited, but examples include a piezo type head and a thermal inkjet type head.

[0104] The object P to be printed is placed on the mounting table 4. A treatment liquid head 1 and an ink head 2 are disposed above the mounting table 4 so that the treatment liquid and ink composition can be ejected onto the object P to be printed. Driven by a motor (not shown), the mounting table 4 moves horizontally in a direction from the treatment liquid head 1 toward the ink head 2 (for example, to the right in FIG. 1 ). The horizontal movement of the mounting table 4 transports the object P to be printed on the mounting table 4.

[0105] The printing object P can be explained in the same manner as the printing object in the ink set described above, and therefore will not be described here.

[0106] In the inkjet printing method (production of a printed item), first, the mounting table 4 on which the item to be printed P is placed moves horizontally, and the item to be printed P is transported to a position facing the treatment liquid head 1. The treatment liquid head 1 ejects (coats) the treatment liquid onto the item to be printed P. The treatment liquid head 1 may eject the treatment liquid only onto the image formation area of ​​the item to be printed P, or onto an area wider than the image formation area of ​​the item to be printed P, or onto the entire surface of the item to be printed P. In order to reduce the amount of treatment liquid used and prevent a deterioration in the feel of the printed item, it is preferable that the treatment liquid head 1 eject the treatment liquid only onto the image formation area of ​​the item to be printed P.

[0107] The amount of the treatment liquid applied to the image formation area of ​​the printing object P is, in mass ratio to the amount of the ink composition applied, 0.5 or more and 1 or less, preferably 0.6 or more and 1 or less, and more preferably 0.7 or more and 1 or less.

[0108] After the treatment liquid is ejected from the treatment liquid head 1, the mounting table 4 on which the object to be printed P is placed further moves horizontally, and the object to be printed P is transported to a position facing the ink head 2. Then, the ink head 2 ejects (applies) the ink composition onto the image formation area of ​​the object to be printed P. In addition to the ink composition, an ink composition of a different color from the ink composition may be ejected from the ink head 2 onto the image formation area of ​​the object to be printed P. In this way, an image is formed by the ink composition in the image formation area of ​​the object to be printed P.

[0109] The amount of the ink composition applied to the image forming area of ​​the printing object P is 20 g / m ２ 80g / m or more ２ Preferably, it is 30 g / m or less. ２ 70g / m or more ２ More preferably, 40 g / m ２ 60g / m or more ２ The following is the result.

[0110]

[0033] Note that, after the treatment liquid has been applied, it is preferable to apply the ink composition without going through a drying step. That is, after both the treatment liquid and the ink composition have been applied, it is preferable to dry the treatment liquid and the ink composition. In this case, reactive aggregation between the water-soluble cationic polymer and organic acid salt in the treatment liquid and the pigment in the ink composition can be more reliably carried out, and as a result, effects such as excellent color development can be achieved. Furthermore, when a post-treatment liquid described below is applied, it is preferable to apply the post-treatment liquid without going through a drying step after the treatment liquid and the ink composition have been applied. That is, after the post-treatment liquid has been applied, it is preferable to dry the treatment liquid, ink composition, and post-treatment liquid. In this case, it is possible to more reliably protect the image obtained by the reactive aggregation described above, and it is possible to improve the fixability and fastness (resistance to rubbing and scraping) of the ink image, etc.

[0111] 2, after the ink composition is ejected from the ink head 2, the mounting table 4 on which the object to be printed P is placed may be further moved horizontally, and the post-treatment liquid may be ejected from the post-treatment liquid head 3. The post-treatment liquid is a non-color-forming treatment liquid that does not develop color even when it adheres to the object to be printed P, and exhibits the function of improving the fixability and fastness (resistance to rubbing and scraping) of the ink image printed on the object to be printed P by the ink head 2. A silicone-based treatment liquid or the like may be used as such a post-treatment liquid. In this way, a treatment film is formed by the post-treatment liquid on the image formed in the image formation area of ​​the object to be printed P. The amount of the post-treatment liquid applied to the image formation area of ​​the object to be printed P is 1 g / m ２ 20g / m or more ２ It is preferable that:

[0112] Next, an example of the textile printing method will be described mainly with reference to Figure 3. Figure 3 is an example of a schematic cross-sectional view of an inkjet printer using the ink set. In the inkjet printer 1000, the feed roller 21 that pays out the work W (textile printing object P) before printing is the winding shaft of the feed roll WA, which is a wound body of the work W before printing. The winding roller 22 is the winding shaft of the winding roll WB, which is a wound body of the work W after the printing process. The winding roller 22 is provided with a first motor M1 that drives the winding roller 22 to rotate about its axis and perform the winding operation of the work W.

[0113] The path between the delivery roller 21 and the take-up roller 22, which passes through the printing area 12, is the transport path (work transport section 200) for the work W. On this transport path, a tension roller 23, a work guide 24, transport rollers 25 and pinch rollers 26, a carry-in roller 27, a dryer 19, and a return roller 28 are arranged in this order from the upstream side.

[0114] The tension roller 23 applies a predetermined tension to the workpiece W upstream of the transport roller 25. The workpiece guide 24 changes the transport direction of the workpiece W from an upward direction to a forward direction, and transports the workpiece W into the printing area 12.

[0115] The transport roller 25 is a roller that generates a transport force that intermittently feeds the workpiece W in the printing area 12. The transport roller 25 is driven to rotate about its axis by the second motor M2, and intermittently transports the workpiece W forward (in a predetermined transport direction F) so that the workpiece W passes through the printing area 12 (image forming position) facing the carriage 30. The pinch roller 26 is disposed opposite the transport roller 25 from above, and forms a transport nip portion with the transport roller 25.

[0116] The feed rollers 27 serve to guide the workpiece W (printed workpiece W) that has passed through the printing area 12 to the dryer 19. The dryer 19 dries the wet workpiece W by blowing warm air onto it or using a heater. In other words, by drying the printed workpiece W, the treatment liquid, ink composition, and post-treatment liquid applied to the printing object P can be dried. Specific drying (heating) conditions include a heating temperature of, for example, 120°C or higher and 180°C or lower. The heating time is, for example, 1 minute or higher and 10 minutes or lower. Heating dries the volatile components contained in the ink composition and treatment liquid, facilitating fixation of the ink composition and treatment liquid to the printing object P. As a result, an image is formed using the ink composition, and a printing object P is formed that has been treated with the treatment liquid.

[0117] The turn-back roller 28 changes the transport direction F of the dried workpiece W from the forward direction to the downward direction, and guides the workpiece W to the take-up roller 22. A platen 29 is disposed below the transport path of the workpiece W in the printing area 12.

[0118] The carriage 30 is supported at one end by the guide rail 17 and moves back and forth in a main scanning direction S (left and right in FIG. 3 ) that intersects with (is perpendicular to) the transport direction F. The carriage 30 includes a carriage frame 30A, and a treatment liquid head 1, an ink head 2, a post-treatment liquid head 3, and a sub-tank (not shown) that are mounted on the carriage frame 30A. The carriage frame 30A includes a head support frame 31 and a back frame 32.

[0119] The head support frame 31 is a horizontal plate that holds the treatment liquid head 1, ink head 2, and post-treatment liquid head 3 described above. The back frame 32 is a vertical plate that extends upward from the rear edge of the head support frame 31 in the transport direction F. The timing belt 16 is fixed to the back frame 32. The guide rails 17 are engaged with the back frame 32. That is, in the example shown in Fig. 3, the back frame 32 is an engagement portion that holds the guide rails 17 in a cantilevered state. The rear end side of the head support frame 31 is held in a cantilevered state by the engagement portion on the guide rails 17.

[0120] The cantilevered state refers to a state in which the engagement portion (back frame 32), which is a portion of the carriage 30 that is held by the guide rail 17, which is a holding member, is present only on one side, either upstream or downstream, from the center of the carriage 30 in the transport direction F, and no other engagement portion is present on the side opposite to the side where the engagement portion is present. The engagement portion may also be located outside the range in which the treatment liquid head 1, the ink head 2, and the post-treatment liquid head 3 are arranged in the transport direction F. In other words, the engagement portion may be located only on the upstream side or only on the downstream side of the range in which the treatment liquid head 1, the ink head 2, and the post-treatment liquid head 3 are arranged in the transport direction F.

[0121] The textile printing method of this embodiment can be implemented by the inkjet textile printing apparatuses 10 and 20 and the inkjet printer 1000 described above, but is not limited to these and can be modified, for example, as shown in the following modified examples. For example, the inkjet textile printing apparatus 10 may be equipped with a sprayer that sprays the treatment liquid instead of the treatment liquid head 1 that ejects the treatment liquid. Alternatively, treatment with the treatment liquid may be performed by immersing the object P to be printed in a tank that stores the treatment liquid. Furthermore, in the inkjet textile printing apparatus 10 described above, the mounting table 4 moves horizontally, but the treatment liquid head 1 and the ink head 2 may move horizontally while the mounting table 4 remains fixed. Alternatively, the mounting table 4 may move horizontally in the transport direction of the object P to be printed, or the treatment liquid head 1 and the ink head 2 may move horizontally while the treatment liquid head 1 and the ink head 2 move horizontally in a direction perpendicular to the transport direction of the object P to be printed.

[0122] As long as the treatment liquid head 1 and the ink head 2 are provided, the effects of the printing method of this embodiment can be obtained regardless of the type of inkjet printing device.

[0123] Summary of the present disclosure An ink set according to a first aspect of the present disclosure is an ink set including an ink composition containing a black pigment and a treatment liquid, wherein the ink composition is applied to an image forming area of ​​a textile printing target at an amount of 20 g / m ２ 80g / m or more ２and the treatment liquid is applied at a mass ratio of 0.5 to 1 relative to the amount of the ink composition applied.

[0124] This ink set can produce printed items with excellent color development, excellent rub fastness, and good texture.

[0125] An ink set according to a second aspect of the present disclosure is the ink set according to the first aspect, wherein the content of the black pigment is 2% by mass or more and 10% by mass or less with respect to the total amount of the ink composition.

[0126] By adopting such a constitution, it is possible to more reliably obtain a printed item having excellent color development and abrasion fastness.

[0127] An ink set according to a third aspect of the present disclosure is the ink set according to the first or second aspect, wherein the ink composition further comprises a resin, an aqueous medium, and an organic solvent, and the resin comprises a first resin having an elongation of 500% or more and 750% or less and a tensile strength of 25 MPa or more and 40 MPa or less, and a second resin having an elongation of 250% or more and 550% or less and a tensile strength of 55 MPa or more and 90 MPa or less.

[0128] By having such a constitution, it is possible to more reliably obtain excellent abrasion fastness and good texture in the resulting printed textile.

[0129] An ink set according to a fourth aspect of the present disclosure is the ink set according to the third aspect, wherein the mass ratio of the first resin to the second resin (the second resin / the first resin) is 0.2 to 1.7.

[0130] By having such a constitution, it is possible to more reliably obtain excellent abrasion fastness and good texture in the resulting printed textile.

[0131] An ink set according to a fifth aspect of the present disclosure is the ink set according to the third or fourth aspect, wherein the first resin and the second resin are polyurethane resins.

[0132] By having such a constitution, it is possible to more reliably obtain a good texture in the resulting printed textile.

[0133] An ink set according to a sixth aspect of the present disclosure is the ink set according to any one of the third to fifth aspects, wherein the total content of the first resin and the second resin is 6% by mass or more and 12% by mass or less with respect to the total amount of the ink composition.

[0134] By having such a constitution, it is possible to more reliably obtain excellent abrasion fastness and good texture in the resulting printed textile.

[0135] An ink set according to a seventh aspect of the present disclosure is the ink set according to any one of the first to sixth aspects, wherein the treatment liquid contains a water-soluble cationic polymer and an organic acid salt, and the total content of the water-soluble cationic polymer and the organic acid salt is 5.0 mass % or more and 40.0 mass % or less with respect to the total amount of the treatment liquid.

[0136] By having such a constitution, it is possible to more reliably obtain excellent color development in the resulting printed textile.

[0137] An ink set according to an eighth aspect of the present disclosure is the ink set according to the seventh aspect, wherein the content of the organic acid salt is 0.1% by mass or more and 25% by mass or less with respect to the total amount of the treatment liquid.

[0138] By having such a constitution, it is possible to ensure a good balance between color development, texture, and abrasion fastness in the obtained printed textile.

[0139] An ink set according to a ninth aspect of the present disclosure is the ink set according to the seventh or eighth aspect, wherein the treatment liquid further contains succinic acid.

[0140] Such a constitution can provide the effect of stabilizing the water-soluble cationic polymer, and the resulting printed textile can have excellent color development and texture while suppressing yellowing.

[0141] An ink set according to a tenth aspect of the present disclosure is the ink set according to any one of the seventh to ninth aspects, wherein the content of the water-soluble cationic polymer is 0.3% by mass or more and 35% by mass or less with respect to the total amount of the treatment liquid.

[0142] By having such a constitution, it is possible to ensure a good balance between color development, texture, and abrasion fastness in the obtained printed textile.

[0143] A textile printing method according to an eleventh aspect of the present disclosure includes applying a treatment liquid to an image formation area to be printed, and applying an ink composition containing a black pigment to the image formation area to which the treatment liquid has been applied, wherein the amount of the ink composition applied to the image formation area is 20 g / m. ２ 80g / m or more ２ and the mass ratio of the treatment liquid to the ink composition is 0.5 or more and 1 or less.

[0144] By adopting such a constitution, it is possible to provide a printing method that can give a printed product having excellent color development, excellent rub fastness, and good texture.

[0145] The present disclosure will be explained in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0146] [Preparation of Treatment Solution] A water-soluble cationic polymer was prepared by ion-exchanging at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) with succinate anions (3.0 parts by mass (solid content)), an organic acid salt was prepared by ion-exchanging ammonium formate (manufactured by Yoneyama Chemical Co., Ltd.) (10 parts by mass), an organic solvent was prepared by ion-exchanging magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) (0.5 parts by mass), an organic solvent was prepared by ion-exchanging "MPD" (manufactured by Kuraray Co., Ltd.) (37 parts by mass), a surfactant was prepared by ion-exchanging "SAG503A" (manufactured by Nissin Chemical Industry Co., Ltd.) (1.0 part by mass), and the remainder was mixed (total 100 parts by mass), and the mixture was filtered through a 5 μm filter to obtain a treatment solution.

[0147] [Preparation of Ink Compositions] (Ink Composition 1) 20 parts by mass of pigment dispersion "AE-2078F" (manufactured by Sanyo Dye Co., Ltd.) (pigment solids content: 4 parts by mass), 30 parts by mass of propylene glycol, 3 parts by mass of urethane resin "Superflex 460 (SF460)" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., tensile strength 25 MPa, elongation 750%) as a first resin, 3 parts by mass of urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as a second resin, 0.8 parts by mass of "Olfine E1004" (manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, and the remainder: water were mixed (total 100 parts by mass), and the mixture was filtered through a 5 μm filter, to obtain ink composition 1.

[0148]

[0122] (Ink composition 2) 25 parts by mass of pigment dispersion "AE-2078F" (manufactured by Sanyo Pigment Co., Ltd.) (pigment solids content: 5 parts by mass), 25 parts by mass of propylene glycol, 5 parts by mass of urethane resin "Superflex 470 (SF470)" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as a first resin, 5 parts by mass of urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as a second resin, 0.8 parts by mass of "Olfine E1004" (manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, and the remainder: water were mixed (total 100 parts by mass), and the mixture was filtered through a 5 μm filter, to obtain ink composition 2.

[0149]

[0122] (Ink composition 3) 15 parts by mass of pigment dispersion "AE-2078F" (manufactured by Sanyo Pigment Co., Ltd.) (pigment solids content: 3 parts by mass), 35 parts by mass of propylene glycol, 2.5 parts by mass of urethane resin "Hydran AP-10" (manufactured by DIC Corporation, tensile strength 36 MPa, elongation 520%) as a first resin, 4 parts by mass of urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as a second resin, 0.8 parts by mass of "Olfine E1004" (manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, and the remainder: water were mixed (total 100 parts by mass), and the mixture was filtered through a 5 μm filter, to obtain ink composition 3.

[0150]

[0122] (Ink composition 4) 30 parts by mass of pigment dispersion "AE-2078F" (manufactured by Sanyo Pigment Co., Ltd.) (pigment solids content: 6 parts by mass), 20 parts by mass of propylene glycol, 9 parts by mass of urethane resin "Superflex 470 (SF470)" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as a first resin, 3 parts by mass of urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as a second resin, 0.8 parts by mass of "Olfine E1004" (manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, and the remainder: water were mixed (total 100 parts by mass), and the mixture was filtered through a 5 μm filter, to obtain ink composition 4.

[0151] The formulations (parts by mass) of ink compositions 1 to 4 are summarized in Table 1.

[0152]

[0153] (Measurement of Tensile Strength and Elongation) The tensile strength and elongation of each of the resins (first resin and second resin) used in Ink Compositions 1 to 4 were measured as follows.

[0154] First, each resin was applied to a PET film so that the film thickness after drying was 500 μm, and then dried at 25° C. and 50% RH for 12 hours, followed by drying at 150° C. for 20 minutes and then peeling off from the sheet to form a resin film.

[0155] Subsequently, the elongation of the obtained resin film was measured using a tensile tester at a measurement temperature of 20° C. and a measurement speed of 200 mm / min. The elongation was measured by stretching the resin film and measuring the length of elongation when the resin film broke, and the percentage was expressed as the elongation.

[0156] The tensile strength of the resin was obtained by measuring the tensile strength of the resin at break.

[0157] In this evaluation, a tensile tester such as "Tensilon Universal Tester RTC-1210A" manufactured by Orientec Co., Ltd. was used.

[0158] [Preparation of post-treatment liquid] 10 parts by mass (solid content) of silicone oil emulsion "POLON-MF-51" (manufactured by Shin-Etsu Chemical Co., Ltd.) with a silicone oil content of 39%, 30 parts by mass of propylene glycol, and the remainder of water were mixed (total 100 parts by mass), and then filtered through a 5 μm filter to obtain a post-treatment liquid.

[0159] [Printing] For inkjet printing, a flatbed printing jig with Kyocera KJ4B heads arranged in the transport direction was used. The treatment liquid was loaded into the first head, one of ink compositions 1 to 4 into the second head, and the post-treatment liquid into the third head, and inkjet printing was carried out under the following conditions and with the application amounts shown in Table 2. - Printing target: polyester (PE) tropical and cotton broadcloth - Printing target / head distance: 3 mm, head temperature: 25°C - Drying: 150°C, 3 minutes (oven)

[0160]

[0161] <Evaluation Tests> PE tropical and cotton broadcloth were used as the printing subjects, and color development tests, texture tests, and abrasion fastness tests were carried out by the methods described below. The results of the evaluation test using PE tropical as the printing subject are shown in Table 3. The results of the evaluation test using cotton broadcloth as the printing subject are shown in Table 4.

[0162] [Color development test] An image in which the treatment liquid, ink composition, and post-treatment liquid were superimposed in this order was measured for color, and an L value of less than 22 was judged as "excellent," 22 or more but less than 26.5 was judged as "pass," and 26.5 or more was judged as "fail."

[0163] [Feel Test] An unused object to be printed was folded in half along the warp (lengthwise), and the distance (loop height) between the lower and upper fabrics at the fold was measured. The measured loop height of the unused object to be printed was taken as the loop height before printing. Next, the area of ​​the printed fabric for evaluation where the solid image was formed was folded in half along the warp (lengthwise), and the loop height was measured. The measured loop height of the printed fabric for evaluation was taken as the loop height after printing. The change rate of loop height (unit: %) before and after printing was calculated according to the formula "change rate of loop height = 100 × loop height after printing / loop height before printing." A lower change rate of loop height indicates that the object to be printed does not harden or swell after printing, and therefore indicates that deterioration in the feel of the printed fabric is suppressed. The evaluation criteria were as follows: less than 130% was "excellent," 130% to less than 150% was "passable," and 150% or more was "fail."

[0164] [Abrasion Fastness Test] The abrasion fastness test of the printed sample was evaluated according to the dry test and wet test of the Abrasion Tester Type II method described in JIS L-0849. After abrasion, the color of the color-transferred area on the cotton fabric was measured at three locations with high color transfer density, and the degree of color transfer was evaluated as the average optical density. The standard was 0.1 for dry abrasion and 0.3 for wet abrasion, and if it was below the standard it was judged as "pass", and if it was above the standard it was judged as "fail".

[0165]

[0166]

[0167] As is clear from Tables 3 and 4, in Examples 1 to 7 in which textile printing was carried out using the ink sets of the present disclosure, printed textiles having excellent color development, excellent rub fastness, and good texture could be obtained.

[0168] The embodiments and examples disclosed herein should be understood to be illustrative in all respects and not restrictive. That is, the scope of the present disclosure includes at least all modifications within the meaning and scope equivalent to the claims. Furthermore, although the comparative examples were inferior in relative evaluation to the examples, this does not mean that the implementation content of the comparative examples themselves is excluded or abandoned.

[0169] According to the present disclosure, it is possible to obtain a printed item having excellent color development, excellent rub fastness, and good texture.

[0170] REFERENCE SIGNS LIST 1 treatment liquid head 2 ink head 2a first ink head 2b second ink head 2c third ink head 2d fourth ink head 3 post-treatment liquid head 4 placement table 10, 20 inkjet printing device P printing object 12 printing area 16 timing belt 17 guide rail 19 dryer 21 feed roller 22 take-up roller 23 tension roller 24 work guide 25 transport roller 26 pinch roller 27 carry-in roller 28 return roller 29 platen 30 carriage 30A carriage frame 31 head support frame 32 back frame 200 work transport section 1000 inkjet printer F transport direction W work WA feed roll WB take-up roll

Claims

1. An ink set comprising an ink composition containing a black pigment and a treatment liquid, wherein the ink composition is applied in an amount of 20 g / m2 to the image forming area of ​​the textile printing object. ２ 80g / m or more ２ and the treatment liquid is applied at a mass ratio of 0.5 to 1 relative to the amount of the ink composition applied.

2. The ink set according to claim 1, wherein the content of the black pigment is 2% by mass or more and 10% by mass or less relative to the total amount of the ink composition.

3. The ink set according to claim 1, wherein the ink composition further comprises a resin, an aqueous medium, and an organic solvent, and the resin comprises a first resin having an elongation of 500% or more and 750% or less and a tensile strength of 25 MPa or more and 40 MPa or less, and a second resin having an elongation of 250% or more and 550% or less and a tensile strength of 55 MPa or more and 90 MPa or less.

4. The ink set according to claim 3, wherein the mass ratio of the first resin to the second resin (the second resin / the first resin) is 0.2 to 1.

7.

5. The ink set according to claim 3, wherein the first resin and the second resin are polyurethane resins.

6. The ink set according to claim 3, wherein the total content of the first resin and the second resin is 6% by mass or more and 12% by mass or less with respect to the total amount of the ink composition.

7. The ink set according to claim 1, wherein the treatment liquid contains a water-soluble cationic polymer and an organic acid salt, and the total content of the water-soluble cationic polymer and the organic acid salt is 5.0% by mass or more and 40.0% by mass or less relative to the total amount of the treatment liquid.

8. The ink set according to claim 7, wherein the content of the organic acid salt is 0.1% by mass or more and 25% by mass or less with respect to the total amount of the treatment liquid.

9. The ink set according to claim 7, wherein the treatment liquid further contains succinic acid.

10. The ink set according to claim 7, wherein the content of the water-soluble cationic polymer is 0.3% by mass or more and 35% by mass or less relative to the total amount of the treatment liquid.

11. A method for printing a textile, comprising: applying a treatment liquid to an image forming area to be printed; and applying an ink composition containing a black pigment to the image forming area to which the treatment liquid has been applied, wherein the amount of the ink composition applied to the image forming area is 20 g / m. ２ 80g / m or more ２ and the mass ratio of the treatment liquid to the ink composition is 0.5 or more and 1 or less.

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